Shaped articles of polypyrrolidone and method of preparation thereof

ABSTRACT

A method of preparing shaped polypyrrolidone articles having a high degree of tensile strength comprising forming said articles from solutions of polypyrrolidone in hydrous formic acid and drawing said articles while impregnated with said hydrous formic acid. The invention also includes the step of enhancing the tenacity of shaped polypyrrolidone articles by impregnation thereof with hydrous formic acid and drawing said impregnated articles.

This is a Division, of application Ser. No. 804,812, filed June 8, 1977,now Pat. No. 4,185,063 which is a continuation-in-part of U.S. Ser. No.687,229, filed May 17, 1976, now abandoned, which is a cont. of Ser. No.547,033 filed Feb. 4, 1975 now abandoned.

BACKGROUND OF THE INVENTION

Polypyrrolidone, formed by the polymerization of 2-pyrrolidone, commonlytermed Nylon-4 is used for the formation of films and fibers of highstrength. Methods for the preparation of polypyrrolidone are describedin U.S. Pat. No. 2,638,463 of May 12, 1953.

It has also been suggested in U.S. Pat. No. 2,711,398 of June 21, 1955to form fibers and films from anhydrous solutions of polypyrrolidone andformic acid. The patent specifies that the utilization of anhydrousformic acid, i.e., 98-100%, is critical to the practice of theinvention.

U.S. Pat. No. 2,889,611 to Bedell of June 9, 1959 discloses thetreatment of various Nylon polymer filaments with strong solutions offormic acid under such conditions that the portion of Nylon dissolved inthe formic acid solution is re-deposited or re-coated upon the externalsurface of the Nylon filament, which treatment increases the flexibilityof the filament without decreasing the tensile strength thereof.

U.S. Pat. No. 3,060,141 discloses a method for preparing shaped articlesfrom aqueous solutions of formic acid. The patent discloses theutilization of aqueous formic acid solutions containing from 10-50% byweight of water.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a composition andmethod for preparing shaped polypyrrolidone articles having highertensile strength and other more desirable properties than those formedaccording to the processes decribed in the above U.S. patents.

These and other objects are achieved by providing a solution ofpolypyrrolidone in hydrous formic acid solution, forming the articlefrom said solution and drawing or stretching the article whileimpregnated with the hydrous formic acid solution to provide articleshaving higher tensile strength and other properties heretoforunattainable in polypyrrolidone materials.

These and other objects are also achieved by impregnating formedpolypyrrolidone articles with hydrous formic acid solutions and drawingor stretching the thus impregnated article in order to increase theirtensile strength and enhance the other properties thereof.

DETAILED DESCRIPTION OF THE INVENTION

It is essential to the practice of the invention that a substantiallyhydrous formic acid solution be employed for forming the polypyrrolidonearticles. More specifically, it is critical to the practice of theinvention that formic acid solutions containing from about 3 to about20% by weight of water to be utilized to form the polypyrrolidonesolutions. Preferably, formic acid solutions containing from 3 to 9% byweight of water have been found to be particularly valuable in formingarticles of the highest tensile strength from polypyrrolidone.

When employing formic acid solutions containing more than about 20% byweight of water, there is a tendency for the solutions to gel. Whenemploying formic acid solutions containing less than about 3% by weightof water, weaker fibers and more opaque films are produced.

In order to achieve satisfactory production of strong fibers, filaments,and films, the ratio of polypyrrolidone to hydrous formic acid solutionsmust be at least about 20% by weight. Obviously, the higher the polymerconcentration in the solution, the more optimum the conditions for theformation of filaments and fibers. As the molecular weight of thepolypyrrolidone employed increases, however, the less polymer is usuallyrequired for the formation of suitable fibers and filaments.

It is preferred to employ solutions comprising from about 1.5 to about 4parts by weight of hydrous formic acid per part of polypyrrolidone. Thisrange has been found suitable for the formation of strong shapedarticles of polypyrrolidone from all molecular weight ranges ofpolypyrrolidone employing 80-97% hydrous formic acid.

It is generally preferred to employ polypyrrolidone having a molecularweight corresponding to a relative viscosity within the range of about 2to about 10, as determined by the relative viscosity of a 1% solutionthereof in metacresol. It is more specifically preferred to employpolypyrrolidone having a relative viscosity of from about 3 to about 6.The most preferred viscosity range is from about 2.5 to about 4.2.

Fairly rapid dissolution of the polypyrrolidone in the hydrous formicacid may be achieved by merely mixing the two materials. However, inorder to speed up solution in the case of the high molecular weightpolypyrrolidone, gentle heating up to about 60° C. may be employed. Athigher temperatures decomposition or depolymerization of thepolypyrrolidone may occur.

Fibers, filaments, and films of suitable denier may be formed byconventional wet- or solution-spinning methods. It is a critical elementof the invention that the fibers, filaments or films formed beimmediately drawn or stretched in order to achieve the highest degree oftensile strength. It has been found that the hydrous formic acidresidues in the shaped articles assist in the drawing process and act toenhance the tensile strength thereof. The precise mechanism behind theenhancement of tensile strength and other properties of the shapedpolypyrrolidone articles is not known. However, the absence of hydrousformic acid residues in the shaped articles during drawing in stretchingresults in articles having markedly lower tensile strengths thanarticles cold drawn in the absence of the hydrous formic acid.

The shaped articles may be prepared without the utilization of heat;however, warm or hot air for purposes of solvent recovery, etc., may beutilized if undertaken at less than about 92° C. for short periods oftime to prevent degradation.

Suitable additives for modifying the properties of the polypyrrolidonemay be included in the polypyrrolidone-hydrous formic acid solutions.For example, Nylon 6 and Nylon 66 or other amidic systems may beincluded in minor proportions to impact various desired properties tothe ultimate shaped articles. Fire retardants, dyes, and other additivesconventionally employed in the plastics industry may also beincorporated.

Films may be formed from the hydrous formic acid solutions ofpolypyrrolidone by any conventional method. The films must then beimmediately drawn or stretched to achieve the highest possible tensilestrength.

As noted above, the invention also includes a method for enhancing thetensile strengths and other properties of shaped polypyrrolidonearticles comprising treating the said articles with an at leastsubstantially hydrous formic acid solution for a period of timesufficient to achieve impregnation thereof followed by drawing orstretching.

It is to be understood that shaped polypyrrolidone articles containingwater may be treated with anhydrous formic acid under conditions suchthat impregnation results in the formation of hydrous formic acidsolutions of the above concentration within the article.

It is conventional in the art of manufacturing fibers, filaments, films,etc., to "cold-draw" the shaped article after it has been formed. It isto be understood that the method of the present invention does notcontemplate "cold-drawing" in the conventional sense. It is critical tothe practice of the invention that the article be impregnated with thehydrous formic acid during the drawing operation. The articles may bedrawn immediately following the method of formation from the hydrousformic acid thereby decreasing the costs involved since it isunnecessary to dry the articles prior to drawing as in the conventionalcold-drawing processes.

The articles formed from the hydrous formic acid solutions or treatedtherewith following formation are drawing from about 100 to about 800%elongation, preferably from about 400 to about 600% elongation.

It is to be understood that when impregnating the already-formedpolypyrrolidone articles, the impregnation may be accomplished utilizingeither solutions of formic acid or vapors thereof. Obviously, theconcentration of the formic acid and the time of immersion are mutuallydependent.

The invention is further illustrated by the following non-limitingExamples.

EXAMPLE 1

One part by weight of polypyrrolidone having a relative viscosity of 4as determined by the relative viscosity of a 1% solution thereof inmetacresol is gradually and slowly dissolved in 4 parts of hydrousformic acid (90% by weight). The solution was agitated until no polymeris visible and until all air pockets have been removed from theresulting viscous solution. Fibers of about 4 denier were wet-spun fromthis solution and immediately drawn about 300% elongation while stillimpregnated with formic acid to yield fibers having 0.93 denier and 33 gper denier tensile strength and 22% elongation at break. The procedurewas carried out in air without the use of a coagulating bath.

Substantially identical fibers from an identical solution which wereonly partially drawn were dried and cold-drawn to the same extentyielding fibers having a tensile strength of only 5.1 g/denier.

Fibers from identical solutions were prepared, only partially drawn,dried and then cold-drawn according to the procedure described above toyield fibers having the following characteristics before and aftersolution-drawing and cold-drawing.

    ______________________________________                                        Tensile Strength                                                                      Drawing Impreg-                                                               nated fibers-          Cold-drawing                                   Denier  Grams per denier                                                                            Denier   Grams per denier                               ______________________________________                                        1.73    16.7          1.90     3.4                                            2.23    19.4          1.55     4.3                                            1.68    24.1          0.26     4.5                                            ______________________________________                                    

The invention includes the shaped polypyrrolidone articles of increasedtensile strength produced according to the above-described process.Generally, these articles possess a tensile strength above 10 grams perdenier.

When treating shaped polypyrrolidone articles to enhance the tensilestrength thereof it is generally preferred to employ hydrous formic acidsolution containing from about 15% to less than about 50% by weight offormic acid.

The time of treatment may vary, depending upon the concentration of thesolution. Generally, when employing the more dilute formic acidsolutions, it is necessary to expose the polypyrrolidone articles to thesolution for a minimum time of about one hour. When utilizing the moreconcentrated solutions, the time of treatment is generally shortenedconsiderably to about 15 minutes or less since longer treatment timeslead to a partial decomposition of the articles. At the lowerconcentrations, there is no danger of decomposition, even over a periodof hours.

It is to be understood that small amounts of acetic acid or other lowercarboxylic acids may be present in the treating solution withoutaffecting the method of the invention.

EXAMPLE 2

Identical melt-spun polypyrrolidone filaments were subjected totreatment with aqueous formic acid solutions of varying strengths forthe purpose of enhancing the tensile strength thereof.

The parameters of the tests and the results thereof are set forth inTable 1 below:

                                      TABLE 1                                     __________________________________________________________________________                    Tenacity                                                                            Percent     Percent                                                     Gram Per                                                                            Increase or                                                                         Elongation                                                                          Increase or                                             Denier                                                                            Denier                                                                              Decrease                                                                            at break                                                                            Decrease                                    __________________________________________________________________________    Control Cold                                                                  Drawn Melt Spun                                                               Nylon 4 (Control)                                                                         3949                                                                              2.2         31                                                TREATMENT                                                                       50% Soln. 5 mins.                                                             immersion then cold                                                           drawn     3000                                                                              2.00  negligible                                                                          28    negligible                                    50% soln. 15 mins.                                                            immersion then cold                                                           drawn     3247                                                                              2.2   none  54    64                                            30% soln. 15 mins.                                                            immersion then cold                                                           drawn     4274                                                                              2.1   negligible                                                                          47    42                                            30% soln. 7 hrs.                                                              immersion then cold                                                           drawn     5860                                                                              3.0   35    50    51                                            30% soln. 30 mins.                                                            immersion then cold                                                           drawn     3792                                                                              2.87  29    50    51                                          __________________________________________________________________________     /

This invention also includes a method for the enhancement of theelastomeric properties of formed polypyrrolidone articles such asfilaments, etc. The method applies to both pre-drawn and drawnfilaments; however, the method is particularly applicable to thetreatment of pre-drawn filaments. Table 1 illustrates the enhancement ofthe elastomeric properties of undrawn filaments.

Generally, the filaments and other shaped articles are treated in thesame manner as described above with respect to the enhancement of thetensile strength of the filaments. The parameters of treatment and theresults of the test as applied to pre-drawn filaments are set forth inTable 2.

It will be understood that filaments or fibers of any size and shape maybe formed according to the method of the present invention. Generally,filaments and fibers having a minimum denier of 0.02 (0.8 microns) maybe prepared according to the present invention.

                  TABLE 2                                                         ______________________________________                                                             Elongation                                                                              Percent                                                       Denier                                                                              Percent   Change                                         ______________________________________                                        Control-Cold Drawn                                                            Melt Spun Nylon 4                                                                              3150    31                                                   Cold Draw Before Immersion                                                    Immersed 25% soln 1 hour                                                                       3924    120       287 gain                                   Immersed 40% soln 2 mins.                                                                      4202    127       311 gain                                   Immersed 50% soln 6 mins.                                                                      3826    70        126 gain                                   Immersed 50% soln 5 mins.                                                                      3789    68        119 gain                                   ______________________________________                                         9n

I claim:
 1. A shaped polypyrrolidone article having a tensile strengthabove 10 grams per denier.
 2. A method of enhancing the tenacity of ashaped polypyrrolidone article comprising contacting said article withformic acid for a time sufficient to at least partially impregnate saidarticle, said formic acid being an at least substantially hydroussolution or capable of impregnating said article and combining withwater present therein to form an at least substantially hydroussolution, and drawing said article while impregnated with said hydrousformic acid.
 3. The method of claim 2 wherein said hydrous solutioncontains from about 15 to about 50% by weight of formic acid.
 4. Themethod of claim 2 wherein said article is drawn from about 100 to about800% elongation.
 5. The method of claim 2 wherein said article is drawnfrom about 400 to about 600% elongation.
 6. The product producedaccording to claim
 2. 7. A method for enhancing the elastomericproperties of a shaped polypyrrolidone article comprising contactingsaid article with formic acid for a time sufficient to at leastpartially impregnate said article, said formic acid being an at leastsubstantially hydrous solution or capable of impregnating said articleand combining with water present therein to form an at leastsubstantially hydrous solution.
 8. The method of claim 7 wherein saidshaped article is pre-drawn.
 9. The product produced by the method ofclaim 7.